Sulfinamides as neutralizers in permanent-waving of the hair



United States Patent 4 3 25s 99s SULFINAMIDES AS I iEUrRALrzaRs INPERMA- NENT-WAVING on THE HAIR Jerome Luloif, East Paterson, andYuma-Hui Chiang,

viously bleached or dyed hair, split or break the hair filaments, andincrease the likelihood of hair being damaged by exposure to sunlight.

This invention provides certain novel neutralizer com- New Milford,lfql, assignors to Shulton, Inc., Clifton, 5 positions containingsulfinamides, some of which are a jl h of New Jersey novel, for use inpermanent waving of hair. Especially No k a 6 1 7 i' 386,058 useful inthe practice of this invention are those sulfinaims amides having theformula: This invention relates to compositions and processes Rs 0 R1useful in the treatment of hair. More particularly it re- 10 g l latesto compounds which are useful as neutralizers for the cold permanentsetting of hair and processes for treat- 34 RI mg half t Suchhefltrhhllhg hp wherein R and R which can be the same or different, TheWttVlhg of hall: e e 'hp e hy atteflhg the and are hydrogen, loweralkyl, lower aminoalkyl, aryl, configuration of the hair wh1le it ismaintained in a curled 15 or, when taken together i h the nitrogen atomto hi h p t In W Waving a Wet Sthand 1S Wound they are attached, amononuclear heterocyclic radical in circular fashion on some sort ofmandrel and allowed such as pyrrohdinyh piperidihyl pipehazinyh H101; todry. The disadvantage of this method isthat the hair phohnyl which canbe substituted i lower lk l remains curled only in the absence ofmo1sture and so groups; R3 is lower alkyl; lower alkylene; l; 1SCommonly eahed a tzh y lhncohtrast P oyl; carbamoyl alkylene, such ascarbamoyl methylene, maheht filial/111g ProduceS 3 Permanent ePresumably carbamoyl ethylene, or carbamoyl propylene; carboxyy alterlhgsome of the ehemleal forces 1n the hall that alkylene, such ascarboxyrnethylene, carboxyethylene, or are stable to water attemperatures normally encountered cal-boXyp1-0py1ene; carboalkoxy, h as-b h y the human ycarboethoxy, or carbopropoxy; carboalkoxyalkylene,Permanent WtlVlhg hasleally Involves a t p P such ascarbomethoxypropylene or carbopropoxymethyle In the first p,Water-Stable chel'hlcal f0Tces aTe ene; carboxy; or N-substitutedcarbamoyl wherein the 111tem1Pted 9 that the'halr y he Set to the dishedsubstituent is lower alkyl, aryl, or carbamoyl groups in P 1Saceoh'lphshed h g h of which the nitrogen is part of a heterocyclic ringwhich lhg lotloh; h whteh 1S Y e t may be monoor polynuclear, such aspyrrolidine, pipera5 the actlVe lhgledlel'lt In wevlhg lotlohs 1Sthlogllfcohc idine, piperazine, morpholine, quinoline or isoquinoline301d, generally 1I1 the form of its salts. After the hair has rings orsuch rings substituted with lower alkyl groups; been softened withwaving lotion and formed 1nto the d R i h d or lower lk L R d R can bdesired configuration, it is necessary to reverse the action the same oriff These substances are d i an of the This reversal 15 31 by f; 35amount effective to neutralize the action of thioglycolic Second hllldwhich 13 eelhlhohly called a heuthahzeracid or other such reducingmaterials contained in the The commonly used neutralizers are chemicaloxidizing permanent waving l i e Ihose I11 use today as e OXidlZlhgIngredient The sulfin-arnides used in the neutralizers of this inven-'1n neutrahzers are hydrogen peroxide and alkaline brotion may b li d toh h i i h form f aqueous mate Salts- 40 solutions or in the form ofemulsions comprising water The af0reh1eht10hed hehtfahzels pp y 'afieetand/or hydrophobic materials, such as glyceride oils. only deslredchemlcal t q groups In the ham Exemplary of sulfinamides which have beenfound usebut since they are HQII- SPBCIfiC OX IdJZPI'S, they appar ntlyful in the practice of this invention are shown -in the 1 1 fig E i ggnolenes, m the ham 2 1i following table Where the generic formula ofthe sulfint ese s1 e-e ec s ave no een senous enough to m e amides istaken for convenience as these substances wholly unacceptable for use ashair wav- 45 ing neutralizers, it has been found that they tend tobleach 0 the hair, oxidize cystine to cysteic acid, damage pre- Q,

TABLE I A 1 R: Z: B.P. na yses percent Remarks c H N -s CZHB N(C2H5)2 C.at 1.30mm. Hg Calm-.. 48.28 10.13 9.39 21.49 0b 48. 25 10.34 9.20 21.18CH N 0 84Cat01 H 01 4414 802 858 1965 mrn. a C

2 5 g Obs.--" 44.37 8.38 8.40 19.30

CH N O 8182Cat024028 rnH v 010 4024 743 939 2149 N2" 3 m g a =l. 00.

Obs 40.53 7.52 9.39 21.23 D 5 2 033 CH N b 79.5 C. at 0.1 mm. Hg0410---- 47.42 8.53 18.09 7.90 Obs 47.05 8.77 18.15 8.00 CH3 C35 011N(C2H5)2 C. at 0.4 mm. Hg 02110...- 51.49 10.50 8.58 19.63 NDW=1.4G20.Cg 0bs 51.26 10.43 8.72 19.92

A preferred water-soluble sulfinamide for the practice of this inventionis (4-morpholinosulfinyl) acetomorpholide:

o 6 J CH2 N O The sulfinamides of this invention are convenientlyapplied to the shaped hair in aqueous solutions or emulsions which maycontain other ingredients commonly used -in commercial neutralizingpreparations, such as glyceride or other oils, emulsifiers, hairconditioners, lubricants, perfumes, and preservatives. The neutralizercompositions can be provided ready for use or as concentrates which arediluted before use.

The sulfinamides of this invention may be present in solution in amountsup to the saturation point of the particular sulfinamide. 1 Whereemulsions are contemplated, amounts beyond saturation point of thesulfinamide can be incorporated. In general, it hasbeen found that verylow concentrations require a long period of time for the neutralizingaction to be complete. On the other hand, the use of excessive amountsof sulfin-amides in the neutralizer serves no useful purpose and merelyincreases the cost of the product.

Generally, it has been found that amounts of sulfinamidein the range offrom about 0.04 mole to the-saturation point of the sulfinarnide in 1000g. of aqueous solutions are satisfactory in the practice of thisinvention. The preferred range of concentrationsis from about 0.2 toabout 1.0 mole of the sulfinamide per thousand grams of total solution.Amounts of (4-mo1-pholinosulfinyl) acetomorpholide on the order of 0.5mole per 1000 g, of solution have been found to give excellent resultsas a neutralizer.

In performing the process of this invention, any of the waving lotionsknown in the art may be used. In addition to the thioglycolic acid andsalts thereof previously mentioned, substances such as, for example,thioglycerol, beta-aminoethyl mercaptan, mercaptoethanol, mercaptobutanesulfonic acid, thioglycolamide, thiolactic acid, sulfites and bisulfidescan be used.

Shaping of the hair to the desired configurations can be achieved byconvention-a1 methods. Curlers of either the spiral rod or croquinoletype may be used. If other styles are desired, clamps of various typesor bobby pins may be employed. If desired, the curling devices can beused in conjunction with end papers.

The sulfinamides of this invention can conveniently be prepared by anumber of reaction routes. for preparing these substances is to react amercaptan with chlorine followed by hydration to form the sulfinylchloride and then to react this with. an aminoor imino- TABLEI-Oontinued Analyses, percent R: Z: M.P., B.P. Remarks o H N s CH NH@0405 Calc 33.62 8.46 13.07 29. 92 Recrystallized Obs 33. 02 8.70 13.1029.71 from ether. C a CH CH CH -N o H (SO-61 0. at 0.25 mm. Hg 04110.-"51.49 10.50 8.58 19. 64

3 a 2 Obs 51. 04 10.50 8.70 19.80 73% yleld.

(311301120114 N 0 88 0. at 0.03 mm. Hg 0900--.. 47.42 3.53 7.90 18.09

0bs. 47.45 8.77 8.10 18.33 80% yield.

on N(CH )4 66O.at6mm.Hg 02110.." 44.41 0.09 10.30 23.72 0bs 44. 33 9. 7710. 47 23. 01 CH3 CHaCHzCHz N(oH3) 55 0. at 1.1 mm. Hg Calc 44.41 9.3910.30 23.72 Obs..-" 44. 64 10.00 10. 05 23. 52

nitrogen-containing substance to obtain the desired sulfinamide. Anothermethod is to react a dicarboxylic disulfide with chlorine andsubsequently with aminoor im-inonitrogen-containing substance. Adisulfide can also be chlorinated and hydrated to form the sulfinylchloride derivative. The first three examples appearing below willillustrate a method for the preparation of a sulfinamide, and thoseskilled in the art will be able readily to apprehend still other routesfor preparing sulfinamides.

In preparing the required intermediate sulfinyl chlorides, it is best touse a 3:1 molar ratio of chlorine to disulfide, except in the case ofdithiodiglycol-ic acid where a 2:1 ratio is preferable. Higher ratios ofchlorine can be used, but amounts of chlorine near the theoretical aregenerally found to produce the best results. Reaction between thechlorine and disulfide is usually effected in a lower alkanoic acid,e.g., acetic or propionic acid using a reaction solvent such asmethylene chloride. A temperature range of from about 20 to 70 C. isuseful, although temperatures somewhat above or below this range may beemployed without adverse effects. In the foregoing temperature rangethereaction is generally completed during a period of "from about one-halfto about three hours. For efiiciency, it is best to agitate the mixtureduring the reaction period, although this is not essential.

The product may be isolated by any convenient procedure. In one methodthe mixture is first allowed to come to room temperature, i.e. about 25C., so as to permit the escape of hydrogen chloride. It is preferred,although not essential, to remove as much as possible of the hydrogenchloride from the reaction mixture. This may be accomplished bymaintaining the mixture at a One method temperature from about 35 C. toabout 60 C. for a brief period of time, e.g. one to two hours. Thereaction mixture is then stripped at subatmospheric pressure at atemperature of from about 50 C. to about 60 C. to leave the desired acidchloride as a residue. The product may be recovered by distillation,preferably at low pressure.

The resulting sulfinyl chloride together with the selected amine orimine is taken up in a reaction-inert organic solvent, such as ahydrocarbon or halogenated hydrocarbon, and particularly lower saturatedor unsaturated hydrocarbon or halogenated hydrocarbons such as hexane,benzene, methylene chloride, ethylene chloride, or

'bromobenzene, and maintained at a low temperature for' a period of fromabout 15 minutes to 3 hours; The preferred temperature range is fromabout -20 to about 5 C., although temperatures somewhat above or belowthis range may be employed.

It is essential that this reaction be run in the absence of air andpreferably in a nitrogen atmosphere.

The product is most simply recovered by filtering ofI the aminehydrochloride and subsequently evaporating the filtrate to dryness underreduced pressure. The product can be purified by distillation orrecrystallization.

Example I A total of 91 grams (0.5 mole) of dithiodiglycolic acid and60.1 grams (1.0 mole) of glacial acetic acid are mixed in a 500 ml.flask fitted with a stirring device, a gas inlet tube extending into theliquid, a gas outlet tube, and a thermometer. The mixture is cooled to70 C. in a solid carbon dioxide-acetone bath and 115 grams (1.5 mole) ofchlorine are introduced during a one-hour period. After the introductionof chlorine the reaction mixture is stirred for an additional halfhour,whereupon the cooling bath is removed and the mixture allowed to come toroom temperature. Finally, the solution is warmed to 40 C. to permit anyremaining hydrogen chloride to escape.

This reaction mixture is distilled at atmospheric pressure to remove allmaterial boiling at temperatures below 54 C. The remaining mixture isthen distilled under reduced pressure to remove acetyl chloride.

The impure sulfinyl chloride so obtained is dissolved in methylenechloride and slowly added to a methylene chloride solution containing174 grams (2.0 moles) of morpholine while cooling with an ice bath andstirring. After the addition of the sulfinyl chloride is complete,stirring is continued for an additional one-half hour. The mixture soobtained is filtered and the filtrate concentrated. The solids obtainedby concentration of the filtrate are combined with the originalprecipitate and crystallized to obtain white crystals melting at 183-185C. This material is then recrystallized from ethanol to obtain acrystalline material with a melting point of 188-189 C. The elementalanalysis shows:

A total of 91 grams (0.5 mole) of dithiodiglycolic acid and 250 ml. ofmethylene chloride are mixed in a 1000 ml. flask fitted with a stirringdevice, a gas inlet tube extending into the liquid, at gas outlet tube,and a thermometer. The mixture is cooled to 20 C. in a solid carbondioxide-acetone bath and 71 grams (1 mole) of chlorine are introducedduring a one-hour period. After the introduction of chlorine thereaction mixture is stirred for an additional half-hour, whereupon thecooling bath is removed and the mixture allowed to come to roomtemperature. Finally, the solution is warmed to 40 C. to permit anyremaining hydrogen chloride to escape.

This reaction mixture is distilled at atmospheric pressure to remove allmaterial boiling at temperatures below 54 C.

The impure sulfinyl chloride so obtained is dissolved in methylenechloride and slowly added to a methylene chloride solution containing348 grams (4.0 moles) of morpholine while cooling with a solid carbondioxideacetone bath and stirring. After the addition of the sulfinylchloride is complete, stirring is continued for an additional one-halfhour. The mixture so obtained is filtered and the filtrate isconcentrated. The solids obtained by concentration of the filtrate arecombined with the original precipitate and crystallized to obtain whitecrystals melting at 183-185 C. This material is then recrystallized fromethanol to obtain a crystalline 5 material with a melting point of188189 C. The elemental anlysi-s shows:

Example III Thirty grams (0.5 mole) of glacial acetic acid, 30.5 grams(0.25 mole) of ethyl disulfide and 200 ml. of dry methylene chloride areintroduced into a 500 ml. fournecked flask equipped with an agitator, -asolid carbon dioxide cooling trap, a gas inlet tube, and a thermometer,and the reaction vessel is immersed in a solid carbon dioxide-acetonecooling bath to maintain the contents of the flask at 0 to 10 C. Then 54grams (0.75 mole) of chlorine are passed into the mixture during a45-minute period. After 30 minutes of chlorine addition, the temperatureis reduced to 10 to 15 C. to minimize evolution of hydrogen chloride andthe attendant loss of chlorine.

After the addition of chlorine has been completed the cooling bath isremoved, and the mixture is permitted to warm to room temperature withcontinued agitation. Vigorous evolution of hydrogen chloride occurs. Themixture is subsequently brought to 35 C. to drive off the remaininghydrogen chloride. The resulting reaction mixture is distilled atatmospheric pressure until it reaches 100 C. and most of the by-productacetyl chloride is removed. The residue is rapidly cooled at temperatureof 20 C. or less and transferred to a smaller flask for distillationunder reduced pressure.

The ethanesulfinyl chloride formed is recovered by collecting thefraction boiling at 485 2 C. at 18 mm. Hg. The yield of this sulfinylchloride is 38.4 grams, or 68.4%

' of theory.

Twenty-two grams (0.3 mole) of diethylamine and ml. of dry methylenechloride are placed in a 500 ml. four-necked flask equipped withagitator, gas cooling condenser, gas inlet tube, thermometer, andpressurebalanced dropping funnel. The gas cooling condenser is filledwith a solid carbon dioxide-acetone mixture and nitrogen was passedthrough the system. The flask is cooled with a solid carbondioxide-acetone bath to maintain an internal temperature'of 0 to 10 C.

A solution of 17 grams (0.15 mole) of ethane sulfinyl chloride in 150ml. of dry methylene chloride is added over a one-hour period. After theaddition is complete,

the cooling bath is removed and the mixture is allowed The(4-morpholinosulfinyl) acetomorpholide obtained in Example I is used tocurl hair according to the technique of Kirby, Waving Efficiency of ColdPermanent Wave Lotion, Drug and Cosmetic Industry, volume 80, Number 3,page314 et seq. (March 1957). In this technique samples of hair arewound through a set of pegs and then successively exposed to a wavinglotion and a neutralizer. The air is removed from the pegs aftertreatment and a measurement of the length is made and compared with theoriginal measurement. The length after treatment with effective coldwaving compounds is iess due to the shortening of the hair strandsbecause of the waves set up therein, and the ratio of lengths before andafter treatment is used to calculate the efiiciency of the materialunder test.

neutralizer (min.) Efficiency, percent The efiiciency value for twentyminutes of treatment compares favorably with values obtained usingpotassium bromate neutralizers in the same test. However potassiumbromate and other known neutralizers do not have the advantages of theneutralizer compositions of this invention, as indicated in thefollowing example.

Example V In a further test, permanents are given to women using thesulfinamide neutralizers of Example I in conjunction with conventionalthioglycolate waving lotions. Solutions of the above-preparedsulfinamide at a concentration of.

0.5 mole/ 1000 g. total solution are used to neutralize the previouslytreated hair for a period of thirty minutes. Compared to standardbromate or peroxide neutralizer results, permanents with the sulfinamideneutralizer of this invention give smoother, -more manageable waveswithout kinkiness or frizzing. Comparable results are obtained with thematerials shown in Table 1.

Although a certain particular embodiment of the invention is hereindisclosed for purposes of explanation, various modifications thereof,after study of this specification will be apparent to those skilled inthe art to which the invention pertains. Reference should accordingly behad to the appended claims in determining the scope of the invention. 7

What is claimed and desired to be secured by Letters Patent is:

1. (4 morpholinosulfinyl) acetomorpholide.

2. Isopropyl sulfinamide.

3. A permanent-waving neutralizer aqueous composition containing 0.2 to1.0 mole per thousand grams of total solution of a sulfinamide selectedfrom compounds having the formula:

' wherein R and R are selected from the group consisting of hydrogen,methyl, ethyl, and when taken together with the nitrogen atom to whichthey are attached, morpholinyl and R is selected from the groupconsisting of hydrogen, methyl, ethyl, propyl, isopropyl, and carbamoylin which the nitrogen atom is part of a morpholine ring.

4. A permanent-waving neutralizer aqueous composition containing 0.2 to1.0 mole per thousand grams of total solution of (4-morpholinosulfinyl)acetomorpholide. 5. In the process of permanent-waving hair whichcomprises treating the hair with a waving lotion, shaping the hair tothe desired configuration, and treating the hair with a neutralizer, theimprovement which comprises using as the neutralizer an aqueouscomposition containing a sulfinamide selected from compounds having theformula:

where R and R are selected from the group consisting of hydrogen,methyl, ethyl, and when taken together with the nitrogen atom to whichthey are attached, morpholinyl and R is selected from the groupconsisting of hydrogen, methyl, ethyl, propyl, isopropyl, and carbamoylin which the nitrogen atom is part of a morpholine ring.

6. The process of claim 5 in which the sulfinamide is(4-morpholinosulfinyl) acetomorpholide.

No references cited.

JULIAN S. LEVITT, Primary Examiner.

3. A PERMANENT-WAVING NEUTRALIZER AQUEOUS COMPOSTION CONTAINING 0.2 TO 1.0 MOLE PER THOUSAND GRAMS OF TOTAL SOLUTION OF A SULFINAMIDE SELECTED FROM COMPOUNDS HAVING THE FORMULA: 